Diastereoselective addition of the 2-phenylsulfonyl-substituted allylic bromides to aldehydes in the presence of zinc or chromium (II) chloride

Tetrahedron Letters,Vo1.27,No.42,pp Printed in Great Britain

DIASTEREOSELECTIVE

ADDITION

TO ALOEHYOES

OF THE 2-PHENYLSULFONYL-SUBSTITUTED

IN THE

P.

PRESENCE

Auvray,

Laboratoire Universiti

P.

OF ZINC

8 M.

Curie,

J.F.

BROMIDES

Normant

Organo-&liments,

4 place

ALLYLIC (II) CHLORIDE

OR CHROMIUM

Knochel*and

de Chimie des

P.

0040-4039/86 $3.00 + .OO Pergamon Journals Ltd.

5091-5094,1986

tour

44-45

Jussieu F-75252 PARIS

CBdex

05

The 2-p&ngL4ui/L1nyi &!&ic bnomide4 1 add diaAe.uudectiv& to vaniow atiehgdu 3 in the iyiaenre of @nc on of in 4ih @ne/reted chmmiwn (11 I 4&4 fo give main.& Me-4y-hydnoxy 4u_l,i?onu 4 *R high yield4. The 4uifone 46 can be eMiCy .tmm4&med into tithe &a,&zneomticaLLg puniT y-pivaloyioxy ketone 14 aUoZng a comp.Le.te corutnol OF the 4teneochemi4tig of foun ad¢ &.&al c&en4 in iK acycLic compound.

%JnrMng :

Scheme

1

+'I

Nu-

R' Recently

We

the

reported

with

report

now that

sulfones

of type -4 reaction

(II)

(see

of zinc3

salts415

scheme

21.

It

selectivity

to

scheme

favored

(iii)

following

reasons

entries

presence

for

the

also

the

or

of type J_ react

functionalized

a metallic

sulfones THF

;

remarkable6

(El-configuration7

highly

a metal*,

of

la-c

0.5hr

;

over

state

bromo-sulfones'

the

of type 1 are

1.5hr

(see

available

produce

R'

able

to

react

salt,

sulfones

regioof

type

regioselectively

to

furnish

the

with

hydroxy-

1).

bromo

THF

of

;

;

the

of type -8 is

to

(generally is

diastereoselectivity

easily

sulfones

(7eq.

(2.0eq.

the (Nu)

presence

of the

diastereoselectivity and

the

-3 in the

presence

that

nucleophiles

Thus the

qph

4,

we have

aldehydes

the

tzLt;j

!?

selectively 2.

Bpr

;

25O)

;

9O:lOl that

1, the

(l.Oeq.1 30°-40") gives the

the

2,

3

aldehydes

the

in

excellent -hydroxy

of

the

intermediate

allylic the

zinc

formation

the

4911

:

the 109“ highly favored.

tfO2Ph

5091

shows

Thus

and the

such

assign highly a chair

in

chromium

(83-99%)

We

which 1.

(1.5eq.1

Ira_j (see

reaction

compound

3a-f

generated

yields

table).

group

of

situ

sulfones

mediated

8

phenylsulfonyl

and

explains

the

in

4p

zinc and

with or of

high table

a

high

this

high

favors

the

transition

-diastereoisomer

4

for

5092

Scheme 2

Table

Synthesis

:

of

chloride

mediated

Bromo-

I

1

IEntry

lsulfone

II

I I

I I

-1

1

12

the

11,

addition

sulfones

of the

4a-j

R'

I

I

Me

I

I

Me I

by

bromo-sulfones

[Aldehydel

1

la

hydroxy

4p

1

la-c

Metal

or

zinc,

1

Products(%)

I

Zn

II &:lOO

I 2:

0

I &:

3

1 cycle-Hex-

I

Zn

I &1:100

1 5b:

0

I

4

I

la

I

Me

I

3c

I

Pent-

I

Zn

1

I

la

I

Me

I

3d

I

tert-Bu-

Zn

( ii:

I5

I

la

IMe

I

tert-Bu-

I (

CrC12

16

1;

I

Me I

g

I

iso-Bu-

I

CrCl2

17

11,

1

Me

I

3f

CrCl2

I

I3d

:E)-CH3-~~=~~-

5

4c:

I

1 6c:

01

91

I

99

I

1 4d:

81

I 5d:

0

1 ;:I91

92

I

I g:

99

I i-i: -

_ 1 Iii01

93

I

90

I

01

83

I

0 I 6J: 01

95

I

67

1 a:33

98

)

94

I

I

ii

Ph-

Zn

I ,:I00

I

Pr

I

ii

Pent-

Zn

I

110

I

Pr

1

ii

Pent-

CrC12

I G:

I 11

I

lb

I

Pr

I

ii-

iso-Bu-

CrC12

I4i:96 -

112

I

Ic

liso-Bul

-3c

Pent-

CrC12

I 4j:

113

I

ii-

I

i3i

I fi:

I

99

1 6d:171

IPr

Pent-

I

01

0

4f:

4h:

&:I2

95

6b:

I 5d:

lb lb

1

l-1 01

I

lb

-3c

-

BB

I

I

I(%Ia I

2

83

I I

Pr

IYield

1 Ph-

salt1

I

chromium

3a-e

&J

[Metal

I3

I9

or

I

I4

18

bismuth

to the aldehydes

3

I-

R2

the

5f:lO

I g:

90

5h:

I 6f:

6

1 $J:

01

6h:

01

I

Isi:4

I6i:Ol

I g:lO

I ;:

0 I -5h:SO

01

I -6h:SOl

93

1

95

I

89

I

37

I

a/ The given yields are those of flash chromatographically purified materials (in all cases the isomers of type 4, 2 and 6 could be separated). TV reactions qr3e performed on a 10mmol scale. All the spectroscopic datas (I-R., H-NMR and C-NMR) are compatible with the structure shown.

Similar

discussions

can

be made

better

diastereoselectivities

result

indicated

isomer

of

type or

assigned

to our major

and 3.

(scheme -4a

The

bismuth9

(see

aldehyde

fi

if

that S

bismuth

entry are isomer

functionalized

3) as a sole

for

isomer

the

(compare leads,

13). used (of

The

chromium

salts

entries

9

although

(see

entries

type

4)

is

tetrahydrofurans by

a

in

regioisomer

5-Endo-Trig

4,

mediated

and

10

low

of

yield,

type

5 and

confirmed

closure"

to

only

The

the

A

relative

even

diastereo

if

a bulky

stereochemistry 10

of

in

obtained

respectively

show

preliminary

anti-

obtained

structures

each

which

table).

only

X-ray

-9a and -9b are ring

the

& is

13). by

reactions

of

of

compounds

high the

yields

sulfones

and -4c.

Scheme -4a

-4c:

:

3 R=Ph R=Pent

KH R

R=Ph

oat.,&

THF;O.Bhr

:

R=Pent

; ;

80% 8g%

5093

The

hydroxy

products

sulfones

of

type

y-hydroxyalkylation

of

11 12-

excess

of nitropropane

Scheme

4

nitrosulfone

12

in

MeOH

then

;

of PhS02H,

Scheme

5

are

to the

81%

the

very

of

sulfone

useful a

from

a dienolate

4b -

; 1 hr

;

NH40Ac(24eq.)

;

(see

diastereoisomerically

;

pure

allow

a

Nef

the

and

Thus,

synthesis

addition

the

derivative

gives,

after

a

enone

13

of

an

hydroxy

reaction I5

y-pivaloyloxy

of

regiospecific

the

gives

pivaloyloxy

by

25')

4).

of DBU13

the

followed 2hr

;

scheme

presence

into

85%)

and

diastereoselective

-10

in the

;

60'

intermediates

formal

type

Transformation

yield.

TiC13c4eq.I

nation

4

resulting of

cat.14

; EiF3.kt2

excess

type

((tBuCO),O

(MeONa(l.5eq.I;

spontaneous in 65%

elimi-

yield.

(65%)

:

1/Me2CuLi e/Me1

(87%)

only Addition excess

of of

of the

isomerI The

scope

adjacent the

CH31

in 87% which

method,

centers

ether

;

(IUeq. -14

-

1 diastereoisomer

(1.5eq.

ketone

of this chiral

relative

in our

Me2CuLi

iodomethane

+pyLEt

;

allows

of

;

0.25

hr) hr

;

followed 25O)

by

leads

l&J the

addition

to only

one

of

an

diastereo-

yield.

in an acyclic

stereochemistry

0.75

;

; -15’ HMPT/THF

Me

all

a complete compound

four

control

(la -- +

centers

in

of

14)

as

ketone

the well

-14

stereochemistry as

are

the

of

four

determination

currently

of

investigated

laboratory.

A*L&em&

-

hi+

pnity,

[on

a pant

IUniven4i.G

We

ihank

ihe

the C. N. W.5. [on to one

of

LU

Vie.i.Ue

,z5nancid

(?'.A.). We

Montage 4uppni

thank

Company (Il. A.

[on a

4731

Pnofe44on

Y.

pnenou4

g.ifi

or &c

and the Rkke-F'oulenc J'ewutin and

Madame

a+!

Cornpang &utuon

$. & IfI.Cuniel {on the X-nag 4tiuctune4.

References and Notes : 1. See the preceding letter

allylic 2. For the

bromides reaction metal : a/

of the 2-phenylsulfonyl-substituted : “An easy synthesis and acetates and their reactivity towards nucleophiles” of functionalized allylic bromides with electrophiles in the presence

K. Reininger and U. Schmidt, Ang. them. 82, 480 (1970) ; of a E. Ohler, Tetrahedron Lett. 23, 3725 (1982) ; T T. Mandai, J. b/J.N. Collard and C. Benezra, Nokami, T. Youro, Y. Yoshinaga and J. Otera, J. Org. Chem. 49, 172 (1984) ; d/ P. Knochel and J.F. Normant, Tetrahedron Lett. 25, 1475, 4383 (1984) ; e/ Y. Okuda, S. Nakatsukasa, K. Oshima and H. Nozaki, Chem. Lett. 481 (1985) ; f/ S.E. Drewes and R.F.A. Hoole, Synth. Commun. 3, 1067 (1985) ; g/ P. Auvray, P. Knochel and J.F. Normant, Tetrahedron Lett. c, 2329 (1985).

5094

3.

4.

5.

6. 7.

8.

9. 10.

Zn a typical reaction, 606mg (2mmol) of the sulfone lb in 4ml THF are slowly added (within 15min) to a THF solution of PhCHO (318mg ; 3mmx ; 2ml THF) and activated zinc ; for the zinc activation see ref. 2d) at 30°-40" in a flask immersed in (Tg ; 15mmol a common laboratory ultrasonic cleaner (48kHz ; 30~). After 0.5hr, the reaction mixture is cooled to O" and quenched with an NH Cl solution. After the usual work-up and a flash-chromatography, the pure hydroxy-sul P one 3 is isolated (630mg ; 95%). Chromium (II) chloride mediated addition of allylic bromides to aldehydes proceeds with good diastereoselectivity : T. Hiyama, K. Kimura and H. Nozaki, Tetrahedron Lett. 22, 1037 (1981) ; T. Hiyama, Y. Okude, K. Kimura and H. Nozaki, Bull. Chem. Sot. Jpn, 55, 561 (1982) ; Y. Okude, S. Hirano, T. Hiyama and H. Nozaki, J. Am. Chem. Sot. 99, 3179 (1977) and C.T. Base and C.H. Heathcock, Tetrahedron Lett. 1685 (1978). In a typical reaction, a THF solution of LiAlH (76mg ; Zmmol) is added to a susoension of CrCl, (630ma : Pmmol : 5ml THF) at -Ito. The resultina dark solution is stirred 15min at 2a"-and 606mg (2mmol) of the bromo sulfone lb in 5ml of THF and then a THF solution of hexanal (336mg ; 3mmol ; 5ml THF) are -&cessively added. After the reaction mixture is cooled to O" and quenched 1.5hr at 25", with an NH4C1 solution. After the usual work-up and a flash-chromatography, two pure products are : 570mg of the 4p -hydroxy sulfone -4h and 35mg of the anti -hydroxy sulfone isolated 5h (total yield : 93%). ne addition of crotyl zinc bromide to aldehydes proceeds with low diastereoselectivity : G. Courtois and L. Miginiac, J. Organometal. Chem. 69, 1 (1974). Usually a 3-substituted allylic bromide is a mixture of (E) and m isomers : see for example : E.G. Hoffmann, H. Nehl, H. Lehmkuhl, K. Seevogel and W. Stempfle, Chem. Ber. 117, 1364 (1984). For an excellent discussion of the configurational stability of ally1 metal compounds and its consequences on the diastereoselectivity in addition reactions see : R.W. Hoffmann, Angew. Chem. 94, 569 (1982) ; Angew. Chem. 21, 555 (1982). H.B. Bijrgi, J.D. Dunitz, J.M. Lehn and G. Wipf, Tetrahedron 30, 1563 (1974) ; A.R. Bassindale, R.J. Ellis, J.C.-Y. Lau and P.G. Taylor, J. Chem. Sot. Chem. Commun. 98 (1986). M. Wada and K. Akiba, Tetrahedron Lett. 26, 4211 (1985). ORTEP representation of compound -9a :

and J.F. Normant, Tetrahedron Lett. 26, 4455 (1985). 11. P. Auvray, P. Knochel y-alkoxy alkylation of aldehyde dienolate equivalents see : A. 12. For a regiospecific cited lshida and T. Mukaiyama, Bull. Chem. Sot. Japan, so, 1161 (1977) and references therein ; see also T. Mukaiyama, Org. React. 3, 203 (1982). For y-hydroxyalkylation 423 (1975) ; M. Gaudemar, of zinc ester dienolates see : M.W. Rathke, Org. React. 2, Organomet. them. Rev. A, s, 183 (1972) ; L.E. Rice, M.C. Boston, H.O. Finklea, B.J. Suder, J.O. Frazier and T. Hudlicky, 1. Org. Chem. 49, 1845 (1984) ; T. Hudlicky, M.G. Natchus, L.O. Kwart and 8.L. Colwell, J. Org. Chem. so, 4300 (1985). A. Kamimura, N. Tsukui and A. Kaji, Tetrahedron Lett. 23, 2957 13. N. Ono, H. Miyake, and A. Kaji, Synthesis, 226 (1984). (1982) ; N. Ono, A. Kamimura and P. Knochel, Tetrahedron 9, 4861 (1985) 14. D. Seebach, G. Calderari and J. Melton, J. Org. Chem. 3, 4367 (1973). 15. ;*Egi ;;M;;rFr C spectrum shows only one diastereoisomer of 14 (purity > 95%). Compare 16. with W.R. Roush and 8.M. Lesur, Tetrahedron Lett. 24, 2231 n983). For the methylation 4450 (1973. see: R.K. Boeckman Jr, J. Org. them. 2,

(Received

in

France

2 July

1986)